CN104538633B - Lithium ion battery electrode material and preparation method thereof - Google Patents

Lithium ion battery electrode material and preparation method thereof Download PDF

Info

Publication number
CN104538633B
CN104538633B CN201410770614.8A CN201410770614A CN104538633B CN 104538633 B CN104538633 B CN 104538633B CN 201410770614 A CN201410770614 A CN 201410770614A CN 104538633 B CN104538633 B CN 104538633B
Authority
CN
China
Prior art keywords
lithium ion
electrode material
ion battery
atom
mixed liquor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201410770614.8A
Other languages
Chinese (zh)
Other versions
CN104538633A (en
Inventor
任景耀
武京湘
任美伦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Huapu New Material Co ltd
Original Assignee
Shenzhen Huapu Intelligent Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen Huapu Intelligent Technology Co Ltd filed Critical Shenzhen Huapu Intelligent Technology Co Ltd
Priority to CN201410770614.8A priority Critical patent/CN104538633B/en
Publication of CN104538633A publication Critical patent/CN104538633A/en
Application granted granted Critical
Publication of CN104538633B publication Critical patent/CN104538633B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/60Selection of substances as active materials, active masses, active liquids of organic compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/06Zinc compounds
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to field of lithium ion battery, particularly to a kind of lithium ion battery electrode material and preparation method thereof.A kind of lithium ion battery electrode material, this electrode material is zinc compound, and chemical formula is C18H18N4O4Zn, wherein zinc compound is rhombic system,PbanSpace group, cell parameter isa=11.937 (8),b=8.935 (2),c=19.074 (2),α=β=γ=90, V=2034.5 (7)3.The zinc compound synthetic method of the present invention is simple, and the Stability Analysis of Structures that selected mixed ligand obtains, when it is as electrode material of lithium battery, in charge and discharge process, it mainly utilizes the atom N on pyrazole ring to carry out the migration of lithium ion for it, so its Stability Analysis of Structures, do not cave in during discharge and recharge.

Description

Lithium ion battery electrode material and preparation method thereof
Technical field
The present invention relates to field of lithium ion battery, particularly to a kind of lithium ion battery electrode material and preparation method thereof.
Background technology
Metal organic framework compound receives extensively due to its variable chemical constitution, excellent character as porous material General concern.By reasonably design, metal organic framework compound can be widely used in gas storage, lithium ion stores, Catalytic field.But, the chemical stability of metal organic framework compound often limits its application in practice, many gold Belong to organic frame compound the most easily decompose or cave in.If in more complicated cases, such as, when It is as the electrode material of lithium ion battery, owing to the situation of electrolyte is increasingly complex, and this metal organic framework compound steady Qualitative worse.
Summary of the invention
The technical problem to be solved is to provide a kind of lithium ion based on metal organic framework compound Battery electrode material.
Further object is that the preparation method that above-mentioned lithium ion battery electrode material is provided.
A kind of lithium ion battery electrode material, this electrode material is zinc compound, and chemical formula is C18H18N4O4Zn, wherein Zinc compound is rhombic system, Pban space group, and cell parameter is a=11.937 (8), b=8.935 (2), c=19.074 (2), α=β=γ=90, V=2034.5 (7)3
The preparation method of above-mentioned lithium ion battery electrode material is: by organic compound 3,3 ', 5,5 '-tetramethyl-4,4 '- Connection pyrazoles, M-phthalic acid, zinc oxide add to the mixed solvent of acetonitrile and water, are stirred at room temperature formation mixed liquor a, Then by described mixed liquor a under the conditions of solvent thermal after reacting by heating slow cooling obtain mixed liquor b;Finally mixed liquor b is existed 7 days described zinc compounds derived above of left at room temperature.
Further, described heating-up temperature is 140 DEG C ~ 160 DEG C, and the reacting by heating time is 24 ~ 48 hours.
Further, described cooling is 2 DEG C/h ~ 5 DEG C/h and is down to room temperature.
Further, described 3,3 ', 5,5 '-tetramethyl-4,4 '-connection pyrazoles, M-phthalic acid, the mol ratio of zinc oxide are 1:1:1。
Further, the volume ratio of described acetonitrile and water is 1:2.
The application in lithium ion battery of the above-mentioned zinc compound.
There is advantages that
The zinc compound synthetic method of the present invention is simple, and the Stability Analysis of Structures that selected mixed ligand obtains, when it During as electrode material of lithium battery, in charge and discharge process, it mainly utilizes the atom N on pyrazole ring to carry out lithium ion for it Migrate, so its Stability Analysis of Structures, do not cave in during discharge and recharge.
Accompanying drawing explanation
Fig. 1 is the zinc compound coordination environment figure with metal center Zn of the present invention.
Fig. 2 is the structural representation of the zinc compound of the present invention.
Fig. 3 is the zinc compound of present invention thermogravimetric curve figure under air atmosphere.
Fig. 4 is that the zinc compound of the present invention is when the cycle performance figure that electric current density is 100mA/g.
Fig. 5 is the zinc compound of present invention high rate performance figure under different electric current densities.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention, It it not limitation of the invention.
Embodiment 1
By 0.2 mmol3,3 ', 5,5 '-tetramethyl-4,4 '-connection pyrazoles, 0.2 mmol M-phthalic acid and, 0.2 mmol Zinc oxide adds to the mixed solvent of 15mL acetonitrile and water (wherein the volume ratio of acetonitrile and water is 1:2), at room temperature stirs Mix formation mixed liquor a, then described mixed liquor a is inserted in 25mL reactor reacting by heating 36 under the conditions of solvent thermal 150 DEG C It is down to room temperature with 3 DEG C/h after hour and obtains mixed liquor b, finally mixed liquor b is at room temperature stood 10 days and obtain described containing zinc Compound, productivity is 58.6% (based on Zn).
Then above-claimed cpd is carried out structural characterization.
The X ray diffracting data of this compound is to visit on diffractometer in Bruker Smart Apex CCD face, uses MoKαSpoke Penetrating (λ=0.71073), collect and carry out Lp factor correction with ω scan mode, absorption correction uses SADABS program.With Direct method solution structure, then obtains whole non-hydrogen atom coordinate by difference Fourier method, and obtains hydrogen atom with theoretical hydrogenation method Position (C H 1.083), is modified structure with method of least square.Evaluation work uses SHELXTL program bag on PC Complete.Compound crystal parameter is shown in Table 1.Structure is shown in Fig. 1, Fig. 2.
Table 1. crystallographic parameter and structure elucidation
From the point of view of crystal structure, this compound belongs to rhombic system, and Pban space group, containing one in this asymmetric cell Zn atom, half 3,3 ', 5,5 '-tetramethyl-4,4 '-connection pyrazoles molecule and half M-phthalic acid molecule, as shown in Figure 1.Its In, Zn atom takes the 6 octahedral patterns of coordination, wherein Zn atom and 2 different 3,3 ', 5,5 '-tetramethyl-4,4 '-connection Atom N coordination on pyrazoles molecule;And the oxygen atom on M-phthalic acid takes pattern and the Zn Atomic coordinate of double coordination;? Eventually, under the interconnection function of M-phthalic acid, define a kind of one-dimensional chain structure as shown in Figure 2, and on pyrazole ring, another does not has The atom N having coordination is then distributed in one-dimensional chain both sides, the beneficially absorption of lithium ion.
Fig. 3 is that the zinc compound of the present invention is risen to 900 DEG C by room temperature with the speed of 10 DEG C/min in air atmosphere Thermogravimetric curve figure, as can be seen from the figure this zinc compound does not has any obvious change from room temperature to 380 DEG C, until 400 DEG C degrees Celsius just start to decompose, and therefore, the zinc compound of the present invention has good stability.
Embodiment 2
By 0.2 mmol3,3 ', 5,5 '-tetramethyl-4,4 '-connection pyrazoles, 0.2 mmol M-phthalic acid and, 0.2 mmol Zinc oxide adds to the mixed solvent of 15mL acetonitrile and water (wherein the volume ratio of acetonitrile and water is 1:2), at room temperature stirs Mix formation mixed liquor a, then described mixed liquor a is inserted in 25mL reactor reacting by heating 48 under the conditions of solvent thermal 140 DEG C It is down to room temperature with 5 DEG C/h after hour and obtains mixed liquor b, finally mixed liquor b is at room temperature stood 7 days and obtain described containing zinc Compound, productivity is 45.9% (based on Zn).
Embodiment 3
By 0.2 mmol3,3 ', 5,5 '-tetramethyl-4,4 '-connection pyrazoles, 0.2 mmol M-phthalic acid and, 0.2 mmol Zinc oxide adds to the mixed solvent of 15mL acetonitrile and water (wherein the volume ratio of acetonitrile and water is 1:2), at room temperature stirs Mix formation mixed liquor a, then described mixed liquor a is inserted in 25mL reactor reacting by heating 24 under the conditions of solvent thermal 160 DEG C It is down to room temperature with 2 DEG C/h after hour and obtains mixed liquor b, finally mixed liquor b is at room temperature stood 8 days and obtain described containing zinc Compound, productivity is 52.6% (based on Zn).
Embodiment 4
Then using above-mentioned zinc compound pulverize after as electrode material, the electrochemical property test of electrode material be by material Material is assembled into button cell (CR-2032) in the glove box of full Ar to be carried out, by active substance, acetylene black and carboxymethyl cellulose Element sodium is dissolved in furnishing mixed slurry in water according to the ratio that mass ratio is 7:2:1 and is coated with on Copper Foil, is dried 12h, punching at 80 DEG C of vacuum Sheet can be prepared by electrode slice.With metal lithium sheet for electrode, 1MLiPF in battery assembling6Be dissolved in EC/DEC (volume ratio is 1: 1) solution is electrolyte, and Celgard 2300 is barrier film, is made into CR-2032 button cell in glove box.Battery is surveyed 12 h need to be stood in room temperature before examination.Charge and discharge cycles test uses LANDCT-2001A battery test system, at voltage under room temperature Scope is to test under 0.1-3.0 V.
Fig. 4 is the zinc compound of the present invention under the 100 mA/g cycle performance figure of first 150 times, from figure, we are permissible Finding out, this zinc compound first circle specific discharge capacity is 248mAh/g, and in ensuing circulation, this zinc compound is always Remain good cyclical stability, specific discharge capacity is always stable at about 152mAh/g, and this is likely due at this containing zinc In compound, the atom N on its special one-dimensional chain structure, the absorption of beneficially Li and desorption, therefore, this zinc compound There is good cycle performance.
Fig. 5 is the high rate performance figure of zinc compound, when electric current density is from 50 to 100, during 200,400 mA/g, and electric discharge ratio Capacity is distributed as 170,150,125,90 mAh/g, and when electric current density returns to 50 mA/g, the capacity of battery remains to return to 170 mAh/g, these results fully show that this zinc compound has excellent high rate performance.
Embodiment described above only have expressed embodiments of the present invention, and it describes more concrete and detailed, but can not Therefore the restriction to the scope of the claims of the present invention it is interpreted as, as long as using the skill that the form of equivalent or equivalent transformation is obtained Art scheme, all should fall within the scope and spirit of the invention.

Claims (3)

1. a lithium ion battery electrode material, it is characterised in that: this electrode material is zinc compound, and chemical formula is C18H18N4O4Zn, this zinc compound is rhombic system, Pban space group, and cell parameter is a=11.937 (8), b=8.935 (2), c=19.074 (2), α=β=γ=90, V=2034.5 (7)3;Described structure cell is asymmetric cell, and this is asymmetric Unit divides containing Zn atom, half 3,3 ', 5,5 '-tetramethyl-4,4 '-connection pyrazoles molecule and half M-phthalic acid Son;Wherein, Zn atom takes the 6 octahedral patterns of coordination, wherein Zn atom and 2 different 3,3 ', 5,5 '-tetramethyl-4, Atom N coordination on 4 '-connection pyrazoles molecule;And the oxygen atom on M-phthalic acid takes the pattern of double coordination and Zn atom to join Position;Its chemical constitution is as follows:
2. the method preparing lithium ion battery electrode material as claimed in claim 1, it is characterised in that: by organic compound Thing 3,3 ', 5,5 '-tetramethyl-4, in the middle of 4 '-connection pyrazoles, M-phthalic acid, zinc oxide addition to the mixed solvent of acetonitrile and water, Be stirred at room temperature formation mixed liquor a, then by described mixed liquor a under the conditions of solvent thermal after reacting by heating slow cooling obtain Mixed liquor b;Finally mixed liquor b is at room temperature stood 7 days described zinc compounds derived above;
Described heating-up temperature is 140 DEG C ~ 160 DEG C, and the reacting by heating time is 24 ~ 48 hours;
Described cooling is 2 DEG C/h ~ 5 DEG C/h and is down to room temperature;
Described 3,3 ', 5,5 '-tetramethyl-4,4 '-connection pyrazoles, M-phthalic acid, the mol ratio of zinc oxide be 1:1:1;
The volume ratio of described acetonitrile and water is 1:2.
3. a lithium ion battery electrode material as claimed in claim 1 application in lithium ion battery.
CN201410770614.8A 2014-12-15 2014-12-15 Lithium ion battery electrode material and preparation method thereof Expired - Fee Related CN104538633B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410770614.8A CN104538633B (en) 2014-12-15 2014-12-15 Lithium ion battery electrode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410770614.8A CN104538633B (en) 2014-12-15 2014-12-15 Lithium ion battery electrode material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104538633A CN104538633A (en) 2015-04-22
CN104538633B true CN104538633B (en) 2016-11-16

Family

ID=52854128

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410770614.8A Expired - Fee Related CN104538633B (en) 2014-12-15 2014-12-15 Lithium ion battery electrode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104538633B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105154980B (en) * 2015-06-19 2017-08-11 福州大学 A kind of anode material of lithium battery and preparation method thereof
CN106356531A (en) * 2015-07-13 2017-01-25 华东师范大学 Cobalt and zinc binary metal coordination polymer, preparation method thereof, application of cobalt and zinc binary metal coordination polymer serving as lithium battery anode material
CN105845938A (en) * 2016-04-04 2016-08-10 陈锦 Electrode material for lithium-ion battery and preparation method of electrode material
CN105633455A (en) * 2016-04-04 2016-06-01 陈锦 Lithium ion battery electrode material and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3558243B2 (en) * 1996-06-27 2004-08-25 矢崎総業株式会社 Rechargeable battery
JP2002216764A (en) * 2001-01-22 2002-08-02 Junko Shigehara Positive electrode material, lithium secondary battery and lithium ion secondary battery using the same
JP4314508B2 (en) * 2002-04-15 2009-08-19 日本電気株式会社 Radical battery
CN101787043B (en) * 2010-02-10 2011-12-28 河北工业大学 Novel light-emitting transition metal organic framework structured compound and preparation method thereof

Also Published As

Publication number Publication date
CN104538633A (en) 2015-04-22

Similar Documents

Publication Publication Date Title
An et al. A flexible ligand-based wavy layered metal–organic framework for lithium-ion storage
Li et al. A highly stable polyoxometalate-based metal–organic framework with an ABW zeolite-like structure
Song et al. Lithium–Lanthanide Bimetallic Metal–Organic Frameworks towards Negative Electrode Materials for Lithium‐Ion Batteries
CN104538633B (en) Lithium ion battery electrode material and preparation method thereof
CN105206879A (en) Alkaline zinc secondary battery and preparation method thereof
CN104307482A (en) Functionalized ZIF type metal organic framework (MOF) porous material as well as preparation method and application of material
CN104393300B (en) The electrode material of lithium ion battery and its application in lithium ion battery
CN103474659A (en) Preparation method and application of positive pole material of sodium-ion battery
CN106946789B (en) two-dimensional porous metal cobalt complex and preparation method and application thereof
Lin et al. Four metal–organic frameworks based on a semirigid tripodal ligand and different secondary building units: structures and electrochemical performance
CN107611439A (en) A kind of preparation method of metal complex lithium ion battery electrode material
CN106299342A (en) Lithium-rich anode material of K ion doping and high-voltage spinel/carbon double-coating and preparation method thereof
CN106025178A (en) Method for preparing metal oxide employing MOF as template and application of metal oxide in negative electrode material of lithium battery
Zhang et al. An alluaudite-type sodium-ion battery cathode candidate Na2Mn2V (PO4) 3: Crystal growth, preparation, structure and electrochemical properties
CN102479944B (en) Preparation method and application of lithium iron phosphate composite material
CN109273714A (en) A kind of preparation and application of the metal-organic framework material with excellent storage lithium performance
CN103450234B (en) A kind of cadmium coordination polymer and preparation method thereof
CN105753072A (en) Lithium nickel manganese oxide as well as preparation method and application thereof
CN107215902A (en) A kind of preparation method of lithium ion battery negative material niobic acid iron
CN104393270B (en) A kind of lithium ion battery electrode material and preparation method thereof
Zak et al. Irreversible anion oxidation leads to dynamic charge compensation in the Ru-poor, Li-rich cathode Li2Ru0. 3Mn0. 7O3
CN106848398A (en) A kind of electrolyte for lithium ion battery
CN110071282A (en) A kind of bismuth phosphate composite reduction graphene oxide composite material and its preparation method and application
CN105024060B (en) Anode material used for lithium ion battery and preparation method thereof
Cheng et al. Four new Zn (ii) and Cd (ii) coordination polymers using two amide-like aromatic multi-carboxylate ligands: synthesis, structures and lithium–selenium batteries application

Legal Events

Date Code Title Description
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C41 Transfer of patent application or patent right or utility model
CB03 Change of inventor or designer information

Inventor after: Ren Jingyao

Inventor after: Wu Jingxiang

Inventor after: Ren Meilun

Inventor before: Liu Guozheng

COR Change of bibliographic data
TA01 Transfer of patent application right

Effective date of registration: 20160906

Address after: 518000, Guangdong, Longhua New District, Shenzhen City, people street, Mei Long Road, Fairview Jiangnan 5 28A

Applicant after: Shenzhen Huapu Intelligent Technology Co.,Ltd.

Address before: North shore village Huang Town Village 523750 ring of Guangdong province Dongguan City Road No. 17

Applicant before: Liu Guozheng

C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20170922

Address after: 518000, Guangdong, Longhua New District, Shenzhen City, people street, Mei Long Road, Fairview Jiangnan 5 28A

Patentee after: SHENZHEN HUAPU NEW MATERIAL CO.,LTD.

Address before: 518000, Guangdong, Longhua New District, Shenzhen City, people street, Mei Long Road, Fairview Jiangnan 5 28A

Patentee before: Shenzhen Huapu Intelligent Technology Co.,Ltd.

TR01 Transfer of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20161116

CF01 Termination of patent right due to non-payment of annual fee